Intermediates for photographic dyes

ABSTRACT

Compounds defined by the following general formula: ##STR1## wherein: X is methyl, methoxy, hydroxy, amino, chloro or carboxy; 
     m is a positive integer from 1 to 2; and 
     A is alkyl having from 9-17 carbon atoms. 
     The compounds of this invention are particularly useful as intermediates for producing photographic dyes.

CROSS REFERENCE TO RELATED APPLICATIONS

This Application is a division of U.S. Pat. application Ser. No. 22,114filed Mar. 30, 1970 (now U.S. Pat. No. 3,925,347) which in turn is aContinuation of application Ser. No. 655,306 filed July 24, 1967 and nowabandoned.

BACKGROUND OF INVENTION

The copending application of Stanley M. Bloom, Ser. No. 655,338 now U.S.Pat. No. 3,751,406, filed concurrently discloses novel chemicalcompounds containing a dye moiety and which also have an "anchoring"moiety which renders the compound immobile and non-diffusible in aphotographic processing composition. Upon oxidation, these compounds mayauto-react intramolecularly in such a way as to form a new heterocyclicring and, as a function of such reaction, to split off the dye moiety asa mobile and diffusible color-providing material.

One group of compounds of this description are represented in thiscopending application as being of the formula: ##STR2## wherein:

EACH OF R and R⁴ comprises a long chain amide, e.g., of at least 13carbon atoms, bonded directly to a nuclear carbon atom or linkedindirectly thereto through an alkylene or phenylene substituent;

D represents a dye moiety, e.g., a monoazo, disazo or anthraquinone dyemoiety; and

N AND N¹ MAY BE 1 OR 2, PROVIDED THAT AT LEAST ONE OF THEM IS 2 TOPROVIDE AN ANCHORING MOIETY; AND NUCLEAR SUBSTITUTED DERIVATIVESTHEREOF, E.G., WHERE ANY OF THE NUCLEAR CARBON ATOMS OF THE RESPECTIVEBENZENE MOIETIES NOT CONTAINING ONE OF THE SPECIFICALLY DESIGNATEDSUBSTITUENTS MAY CONTAIN A CARBOXY, ALKYL, ALKOXY, AMINO, CHLORO,HYDROXY OR AMIDE SUBSTITUENT.

Such compounds may be prepared by the following sequence of reactions:##STR3##

The aforementioned compounds are of particular use in the photographicsystems for preparing color images which are described and claimed inthe copending applications of Stanley M. Bloom and Howard G. Rogers,Ser. No. 655,440 now U.S. Pat. No. 3,443,940; Stanley M. Bloom andRobert K. Stephens, Ser. No. 655,501 filed July 24, 1967 and nowabandoned and Stanley M. Bloom and Robert K. Stephens, Ser. No. 655,436now U.S. Pat. No. 3,443,939, all filed concurrently.

The present invention is directed to novel procedures for preparingcompounds of the foregoing description, which procedures greatlyfacilitate synthesis of the desired compound and in fact make itpossible to obtain readily certain compounds of the above-mentionedformula which can only be obtained with great difficulty, if at all.

SUMMARY

According to the present invention, compounds within the above-mentionedformula may be readily obtained by employing a methoxymethoxysubstituent in lieu of a methoxy substituent as the protected hydroxygroup in the above sequence of steps. The desired hydroxy group may bereadily obtained by hydrolysis, e.g., with a mineral acid such as HCl.

The novel procedures of this invention may be employed in conjunctionwith the procedures described and claimed in the copending applicationof Harris L. Curtis, Ser. No. 655,304 filed July 24, 1967 and nowabandoned filed concurrently and directed to a novel synthesis ofcertain compounds within the scope of the above formula.

As was mentioned previously, this invention relates to novel proceduresfor preparing compounds useful in photographic processes for preparingcolor images.

A primary object of this invention, therefore, is to provide novelprocedures of the foregoing description.

Another object is to provide novel intermediates which may be readilyhydrolyzed to obtain compounds containing a dye moiety and which alsohave an anchoring moiety rendering the compound immobile andnon-diffusible in a photographic processing composition, whichcompounds, upon oxidation, may auto-react intramolecularly in such a wayas to form a new heterocyclic ring and, as a function of such reaction,split off the dye moiety as a mobile and diffusible dye.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the several steps and the relationand order of one or more of such steps with respect to each of theothers, and the product possessing the features, properties and therelation of elements which are exemplified in the following detaileddisclosure, and the scope of the application of which will be indicatedin the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description.

The novel process of this invention by which the aforementionedobjectives are accomplished may be illustrated by the following sequenceof steps: ##STR4##

In the above sequence of reactions, R, n and D have the meaningsheretofore noted, X is an alkyl radical, e.g., methyl, an alkoxyradical, e.g., methoxy, hydroxy, amino, chloro, or carboxy; and m is apositive integer from 1-5, inclusive, it being understood that where mis 1, hydrogen atoms are bonded to the respective four unsubstitutedcarbon atoms.

The process of this invention may be employed in conjunction with theprocedures described and claimed in the aforementioned application ofHarris L. Curtis, Ser. No. 655,304 filed July 24, 1967 and now abandonedto prepare certain compounds within the scope of formula B, whichcompounds may be represented by the formula: ##STR5## wherein D, X and mhave the meanings heretofore noted, and

A is an alkyl radical of at least nine carbon atoms.

The synthesis of compounds within the scope of formula (C) may beillustrated as follows: ##STR6##

The starting p-methoxymethoxy-anilines of step I in the above two setsof reaction sequences are in general known in the art. They may beprepared by replacing the hydrogen atom of the hydroxyl moiety of thecorresponding p-nitrophenol with a --CH₂ OCH₃ substituent in knownmanner, e.g., methoxymethylation by reaction of the nitrophenol withClCH₂ OCH₃ followed by catalytic hydrogenation to reduce the nitro groupto an amino group to provide the desired methoxymethoxy compound.P-nitrophenols from which the starting protected derivative(methoxymethoxy derivative) may be obtained may be selected from thoseheretofore known in the art, e.g., p-nitrophenol,4-nitro-2-methylphenol, 4-nitro-2-methoxyphenol,4-nitro-2-carboxyphenol, 4-nitro-2-chlorophenol,4-nitro-2,6-dimethylphenol, 4-nitro-2,6-dimethoxyphenol,4,6-dinitro-2-methylphenol, 4-nitro-2-ethoxyphenol,4-nitro-2-propoxyphenol, 4-nitro-2-butoxy-phenol, 4-nitro-2-amylphenol,4-nitro-3-methylphenol, 4-nitro-3-ethylphenol,4-nitro-3-penta-decylphenol, 4-nitro-3-decylphenol,4-nitro-2,6-dichlorophenol, 4-nitro-2-methoxy-6-methyl-phenol,4-nitro-2-ethoxy-6-methyl-phenol, 4-nitro-2-methyl-6-propylphenol,4-nitro-2,3-dimethylphenol, 4-nitro-3,5-dimethyl-phenol,4-nitro-3-methyl-5-propyl-phenol, 4-nitro-2,5-dimethylphenol,4-nitro-2-isopropyl-5-methylphenol, 4-nitro-2,5-dimethoxyphenol, etc.

The reduction of step II (as well as the aforementioned reduction of thenitro group following methoxymethylation) may be performed byhydrogenation in the presence of a catalyst, i.e., introducing hydrogengas into a mixture containing the nitro compound and one of the knownhydrogenation catalysts, e.g., Pd/BaSO₄, Raney nickel, etc.

The dye sulfonyl chloride may be a sulfonyl chloride of any of themonoazo, disazo or anthraquinone dyes heretofore known in the art andmay comprise any of the dye moieties disclosed in the aforementionedcopending application Ser. No. 655,338 now U.S. Pat. No. 3,751,406. Ingeneral, dyes containing a sulfonyl chloride substituent making themuseful in the practice of this invention are well known. Accordingly, along list of useful dyes which may be employed will be readily suggestedto those skilled in the art. The preparation of such dyes is describedin numerous texts and therefore will also be apparent to those skilledin the art. (See, for example, "Synthetic Dyes" by Venkataraman, 1952,Vol. I, pp. 197-201.)

The removal of the methoxymethyl protective group to form the desiredhydroxy substituent may be readily accomplished by hydrolysis, e.g.,with a mineral acid such as HCl in a suitable organic solvent such asmethanol, ethanol, methyl cellosolve, etc.

The various reaction conditions, e.g., time, temperature and pressure ofreaction, selection of solvents to form the reaction mixture, etc., arenot essential to the practice of this invention and will be readilyapparent to those skilled in the art in the light of the foregoingdescription. The essence of the invention is, therefore, theaforementioned selection of steps, in the order described, to obtain thedesired dyes.

Where the dye employed is a metal-complexable dye, e.g., an azo dyehaving chelatable groups such as hydroxy or carboxy groups ortho, ortho'to the azo linkage, the present invention is adaptable to thepreparation of metal complexes of dyes within formula (B), e.g.,chromium, nickel, copper, etc., complexes. The dye may bemetal-complexed either before or after removal of the protected group toform the corresponding hydroxy analogue. For example, the chromiumcomplex of a dye of formula (B) may be formed by reaction between asuitable chromium salt, e.g., chromium chloride and the methoxymethoxyanalogue of a complexable dye of formula (B), in known manner forformation of chromium complexes, followed by hydrolysis to form thedesired compound.

As examples of compounds within the scope of formula (B) which may beprepared by the present invention, mention may be made of the following:##STR7##

The following Examples show by way of illustration and not by way oflimitation the practice of this invention.

EXAMPLE 1

Fifteen grams of 4-fluoro-5-nitro-aniline, 35.0 g. of stearoyl chlorideand 8.4 g. of sodium bicarbonate were stirred overnight at roomtemperature. The reaction mixture was then refluxed and the insolubleinorganic salts were filtered off. Upon cooling of the filtrate,2-fluoro-5-stearamido-nitrobenzene, an off-white solid was obtained,m.p. 82-83° C., of the formula: ##STR8## 8.0 g. of the above compound,14.5 g. of p-methoxymethoxyaniline, 4.0 g. of magnesium oxide and 100.0ml. of water were heated in a bomb with shaking at 180° C. for 2 days.After cooling, the contents were filtered and the solid obtained therebywas recrystallized from ethyl acetate to yield 6.0 g. of an orangecrystalline solid, m.p. 118°-119° C. of the formula: ##STR9## 6.0 g. ofthe last-mentioned compound was hydrogenated in ethyl acetate using 5%palladium on barium sulfate as catalyst. After theoretical uptake wascompleted, the reaction mixture was heated to boiling and filteredthrough celite. After cooling, the filtrate was again filtered to yield4.0 g. of the corresponding amine, a white solid, m.p. 113°-114° C. 5.4g. of this amine (prepared in the above manner) and 4.9 g. of:1-phenyl-3-methyl-4-(4'-chlorosulfonyl-2'-acetoxynaphthalene-1')azopyrazolone-5-onein 100 ml. of pyridine were heated overnight on a steam bath. Themixture was then poured into 300.0 ml. of 10% sodium bicarbonate andabout 50.0 g. of ice. The resulting red solid was filtered andrecrystallized from methanol to yield 5.0 g. of a sulfonamide, m.p.139°-141° C. of the formula: ##STR10##

The above compound may be hydrolyzed by stirring in hot 10% hydrochloricacid and then filtering to yield the compound of formula 1.

EXAMPLE 2

5.0 g. of the methoxymethoxy analogue of the compound of formula 1(prepared as in Example 1) and 3.0 g. of chromium chloride were refluxedovernight in 100 ml. of ethanol. The solvent was removed in vacuo andthe residue was then dissolved in hot chloroform and filtered. Thechloroform was evaporated and the resulting magenta solid was stirred inhot 10% HCl and filtered to yield 3.0 g. of the chromium complex offormula 2.

By way of recapitulation, the present invention is directed to a novelsynthesis of a class of compounds described and claimed in theaforementioned copending application Ser. No. 655,338, which compoundsare of particular use in color photography. In the preparation of thesecompounds it is necessary that the phenolic hydroxy group be protectedduring synthesis. The desired compound is finally obtained by removal ofthe protective groups.

In the aforementioned application Ser. No. 655,338 now U.S. Pat. No.3,751,406, the phenolic hydroxy group is protected by methylation.Subsequent removal of the protective group to form the correspondinghydroxy analogue requires strong reaction conditions, e.g., by reactionwith boron tribromide, which in many instances make it extremelydifficult, if not impossible, to prepare certain compounds within theclaimed class. These strong reaction conditions at times result inunwanted substitution of other desired moieties of the molecule and mayeven result in cleavage of the compound, thereby precluding formation ofthe desired compound.

By the present invention, these difficulties in synthesis are completelyobviated by employing a methoxymethoxy substituent as the protectivegroup in lieu of a methoxy substituent. The methoxymethoxy substituent,it has been discovered, may be readily removed by hydrolysis under mildconditions, e.g. with a mineral acid, which do not result in any adverseside reactions.

Since certain changes may be made in the above product and processwithout departing from the scope of the invention herein involved, it isintended that all matter contained in the above description shall beinterpreted as illustrative and not in a limiting sense.

I claim:
 1. A compound of the formula: ##STR11## wherein: X is methyl,methoxy, hydroxy, amino, chloro or carboxy; m is a positive integer from1 to 2; and A is alkyl having from 9-17 carbon atoms.
 2. A compound ofclaim 1 of the formula: ##STR12##
 3. A compound of the formula ##STR13##wherein: X is methyl, methoxy, hydroxy, amino, chloro or carboxy; m is apositive integer from 1 to 2; and A is alkyl having from 9-17 carbonatoms.
 4. A compound of claim 3 of the formula: ##STR14## .